CN106189953A - A kind of Ludox soybean-based sheet material adhesive and preparation method thereof - Google Patents

A kind of Ludox soybean-based sheet material adhesive and preparation method thereof Download PDF

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Publication number
CN106189953A
CN106189953A CN201610656551.2A CN201610656551A CN106189953A CN 106189953 A CN106189953 A CN 106189953A CN 201610656551 A CN201610656551 A CN 201610656551A CN 106189953 A CN106189953 A CN 106189953A
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soybean
minute
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temperature
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毕全中
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Quanjiao Haifeng Printing Packaging Co Ltd
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Quanjiao Haifeng Printing Packaging Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H1/00—Macromolecular products derived from proteins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Materials Engineering (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention discloses a kind of Ludox soybean-based sheet material adhesive, it is made up of the raw material of following weight parts: polyvinyl alcohol 24, defatted soybean flour 170 200, iron chloride 0.3 0.4, ferrous chloride 0.1 0.2, epoxychloropropane 0.8 1, N n-methylolacrylamide 23, styrene 16 20, potassium peroxydisulfate 0.1 0.2, hemicellulase 34, poly-methyl diphenylene diisocyanate 10 19, the hydrochloric acid solution 60 70 of 20 30%, pyromellitic acid dianhydride 0.6 1, Sodium fluoroborate 23, tetraethyl orthosilicate 68, hexadecyltrimethylammonium chloride 0.7 1, nylon acid methyl ester 23, calcium stearate 12.The present invention is difficult to cause equipment corrosion, working life to deposit the features such as phase longer, formaldehydeless, residual monomer content is low, the feature of environmental protection, water-tolerant.

Description

A kind of Ludox soybean-based sheet material adhesive and preparation method thereof
Technical field
The present invention relates to adhesive technical field, particularly relate to a kind of Ludox soybean-based sheet material adhesive and preparation side thereof Method.
Background technology
Aldehyde system adhesive consumption in timber industry adhesive is maximum, but it exists shortcomings: primary raw material multi-source In the non-renewable resources such as oil, coal;Produce and use process constantly distributes carcinogen (such as formaldehyde), can be good for by harmful to human Health;Product non-degradable, easily pollutes environment.Therefore, biomass-based adhesive is researched and developed to substitute aldehyde system adhesive by the whole world Pay much attention to.In various biological materials, Semen sojae atricolor (including genetically engineered soybean) has that yield is big, low cost, vegetable protein contain Measure high feature, be good adhesive raw material;Research soybean-based adhesive so that it is all or part of petroleum replacing base gluing Agent, to reduce depletion of non-renewable resources, ensure food safety the most significant, be outside Present Domestic research focus；
Adhesive the most nontoxic, free of contamination is applied to become trend, plant along with using the exploitation of reproducible biomass from producing to The research of albumen adhesive causes the extensive concern of people.Wherein, utilizing soybean protein to prepare soybean-based adhesive is study hotspot, Improving its resistance to water is then primary study content, and it is the most resistance to that oneself there are some researches show that adhesive prepared by soybean protein isolate has Aqueous；But, SPI is isolatable from Semen sojae atricolor defatted soy flour, and the price of its costliness necessarily limits its application in terms of adhesive.Cause This, the DSF of cost and low percentages of protein becomes the preferred raw materials preparing water-resistant soybean base adhesive；
SPI and DSF, SPI that after preparation soybean-based adhesive mainly uses soybean extract oil at present, defat bean cypress produces derive from DSF, its soybean protein content is typically larger than 90%, it is easy to modified, the adhesive of preparation has good resistance to water.But SPI costliness Its application in terms of adhesive of price limit.Therefore, the DSF of cost and low percentages of protein become preparation resistance to water big The preferred material of bean base adhesive.A large amount of research methoies based on SPI adhesive are also used for modified DSF and prepare adhesive, and Achieve certain effect, it is thus achieved that low resistance to water (cold water or humid air), medium resistance to water (63 DEG C of water) and enhanced water resistance The modified soybean base adhesive formula of (boiling water);Wherein, enhanced water resistance soybean-based adhesive is mainly by excellent with boiling water resistance energy Obtain after different synthetic resin mixing.But, DSF is complicated mixture, by the soybean protein of nearly 50%, the carbon hydrate of 40% Thing and other micro constitutent form；
Current research method all lays particular emphasis on modified soybean protein therein, and is not directed to the carbohydrate of 40%, causes this Resistance to water after adhesive is solidified by component is inoperative, even plays negative interaction, wastes raw material.Additionally, have resistance to boiling Aqueous can be adhesive for making the precondition of outdoor cementing thing, if when with DSF glue so that it is in carbon hydrate Thing converts the component that raising adhesive resistance to water rises positive interaction, in conjunction with Soybean Protein Modification method, prepares the bean of resistance to boiling water base Adhesive, not only takes full advantage of raw material, can be also that a new way is opened up in the soybean-based adhesive research being applied to open air. The research solving problem that aldehyde system adhesive exists and the based Wood Adhesives that instructs other similar biomass to be raw material is all anticipated by this Justice is great；
Epoxy radicals is the polar group that a kind of work is dialled, and can form chemistry and be bonded with the radical reaction containing active oxygen, utilize containing epoxy The compound on organism matter adhesive of group is modified improving research existing many reports of its performance, if therefore used Containing epoxy compounds, it is modified, or access ring epoxide in the component containing these functional groups, necessarily can carry further High Semen sojae atricolor base adhesive resistance to water.
Summary of the invention
The object of the invention is contemplated to make up the defect of prior art, it is provided that a kind of Ludox soybean-based sheet material adhesive and Its preparation method.
The present invention is achieved by the following technical solutions:
A kind of Ludox soybean-based sheet material adhesive, it is made up of the raw material of following weight parts:
Polyvinyl alcohol 2-4, defatted soybean flour 170-200, iron chloride 0.3-0.4, ferrous chloride 0.1-0.2, epoxychloropropane 0.8-1, N hydroxymethyl acrylamide 2-3, styrene 16-20, potassium peroxydisulfate 0.1-0.2, hemicellulase 3-4, poly-diphenyl The hydrochloric acid solution 60-70 of methane diisocyanate 10-19,20-30%, pyromellitic acid dianhydride 0.6-1, Sodium fluoroborate 2-3, positive silicon Acetoacetic ester 6-8, hexadecyltrimethylammonium chloride 0.7-1, nylon acid methyl ester 2-3, calcium stearate 1-2.
The preparation method of a kind of described Ludox soybean-based sheet material adhesive, comprises the following steps:
(1) by above-mentioned iron chloride, ferrous chloride mixing, join in the hydrochloric acid solution of 20-30%, stir, obtain iron salt molten Liquid；
(2) by above-mentioned hexadecyltrimethylammonium chloride, Sodium fluoroborate mixing, join compound weight 28-30 times go from In sub-water, stirring, rise high-temperature and be 70-76 DEG C, insulated and stirred 10-15 minute, the hydrochloric acid of dropping 96-98%, regulation pH is 2-3, continues insulated and stirred 20-30 minute, adds above-mentioned calcium stearate, and stirring, to room temperature, obtains acid dispersion；
(3) above-mentioned tetraethyl orthosilicate is joined in the deionized water of its weight 17-20 times, stir, add PMA Dianhydride, rises high-temperature and is 60-67 DEG C, add above-mentioned acid dispersion, insulated and stirred 1-2 hour, obtain silicon dispersion liquid；
(4) above-mentioned defatted soybean flour is joined in the distilled water of its weight 20-27 times, stirs, add hemicellulase, Enzymolysis 18-20 minute at 50-55 DEG C, reduces temperature and is 26-30 DEG C, add above-mentioned iron salt solutions, be incubated 30-35 minute, add Entering the sodium hydroxide of 3-5mol/l, regulation pH is 5-6, adds above-mentioned epoxychloropropane, rises high-temperature and is 70-75 DEG C, and insulation is stirred Mixing 30-35 minute, add the sodium hydroxide of 3-5mol/l, regulation pH is 10-11, stirring reaction 30-40 minute, obtains epoxide modified Semen sojae atricolor latex；
(5) take above-mentioned epoxide modified Semen sojae atricolor latex, be passed through nitrogen, rise high-temperature and be 70-75 DEG C, add above-mentioned N-methylol propylene Amide, drips acetic acid, and regulation pH is 5-6, and insulated and stirred 60-60 minute obtains acid amide-grafted epoxy soybean latex；
(6) take above-mentioned acid amide-grafted epoxy soybean latex, mix with silicon dispersion liquid, add nylon acid methyl ester, be incubated at 80-90 DEG C Stir 10-15 minute, add above-mentioned polyvinyl alcohol, rise high-temperature and be 76-80 DEG C, insulated and stirred 20-30 minute, add above-mentioned benzene The 20-25% of weight ethylene, the 18-20% of above-mentioned potassium peroxydisulfate weight, stirring mixing 10-20 minute, drip remaining styrene, Potassium peroxydisulfate, reduces temperature and is 40-45 DEG C, insulation reaction 60-70 minute, cooling, obtains Polystyrene grafting rubber made from soybean cake；
(7) above-mentioned Polystyrene grafting rubber made from soybean cake is mixed with remaining each raw material, stir, to obtain final product.
The invention have the advantage that using method:
During use, adhesive of the present invention 2-poly-with the firming agent of its weight 8-10% phenylmethane cyanate (PMDI) is mixed, stir Mixing uniformly, be coated on plate surface, plate surface coating amount is 280 g/m2, and after gluing, room temperature Guan Bi ageing 10 min, are re-fed into Press, sheeting process is: room temperature, 4.0 MPa, 40 min,.
First defatted soybean flour is used hemicellulose ferment treatment by the present invention, then by acid, alkali, salt Combined Treatment, can be by big Soybean protein partial hydrolysis, destroys oxygen key, unfolds the chondritic of soybean protein so that it is active center is exposed, and improves in adhesive The content of active function groups and reactivity, can form preferably crosslinking, thus improve its water resistance after causing its solidification, And the Semen sojae atricolor latex after hemicellulose ferment treatment contains substantial amounts of active group, such as-NH2 ,-C00H ,-OH etc., can be with epoxy chlorine Epoxy radicals generation chemical reaction in propane, is conducive to eliminating the hydrophilic radical in soybean-based adhesive, is cross-linked into said three-dimensional body Type structure, improves the resistance to water after its solidification, then utilizes methylol and the epoxy soybean base gluing of N hydroxymethyl acrylamide Agent contains the component reaction of these functional groups, forms grafting, and the vinyl in N hydroxymethyl acrylamide can be with styrene Monomer forms stable copolymer, and after styrene copolymerized, vinyl residual quantity declines, the phenyl in polystyrene structure, alkane Hydrocarbon methyl composition increases, and improves the stability of modified soybean base adhesive, and only containing phenyl, parent in styrene molecules structure Aqueous is little；Meanwhile, the more preferable phenyl ring of a large amount of stability is introduced into modification by copolymerization soybean-based adhesive, causes its resistance to water to improve. The styrene copolymerized modified soybean base adhesive of the present invention is difficult to cause equipment corrosion, working life to deposit, and the phase is longer, do not contain The features such as formaldehyde, residual monomer content are low, the feature of environmental protection, water-tolerant
Present invention adds tetraethyl orthosilicate is Ludox prepared by raw material, and the bonding that can effectively improve finished product adhesive is strong Degree and toughness, improve stability_intensity.
Detailed description of the invention
A kind of Ludox soybean-based sheet material adhesive, it is made up of the raw material of following weight parts:
Polyvinyl alcohol 2, defatted soybean flour 170, iron chloride 0.3, ferrous chloride 0.1, epoxychloropropane 0.8, N methylol acryloyl Amine 2, styrene 16, potassium peroxydisulfate 0.1, hemicellulase 3, the hydrochloric acid solution of poly-methyl diphenylene diisocyanate 10,20% 60, pyromellitic acid dianhydride 0.6, Sodium fluoroborate 2, tetraethyl orthosilicate 6, hexadecyltrimethylammonium chloride 0.7, nylon acid methyl ester 2, Calcium stearate 1.
The preparation method of a kind of described Ludox soybean-based sheet material adhesive, comprises the following steps:
(1) by above-mentioned iron chloride, ferrous chloride mixing, join in the hydrochloric acid solution of 20%, stir, obtain iron salt solutions；
(2) by above-mentioned hexadecyltrimethylammonium chloride, Sodium fluoroborate mixing, the deionized water of compound weight 28 times is joined In, stir, rising high-temperature is 70 DEG C, insulated and stirred 10 minutes, the hydrochloric acid of dropping 96%, and regulation pH is 2, continues insulation and stirs Mixing 20 minutes, add above-mentioned calcium stearate, stirring, to room temperature, obtains acid dispersion；
(3) above-mentioned tetraethyl orthosilicate is joined in the deionized water of its weight 17 times, stir, add PMA two Acid anhydride, rising high-temperature is 60 DEG C, adds above-mentioned acid dispersion, insulated and stirred 1 hour, obtains silicon dispersion liquid；
(4) above-mentioned defatted soybean flour is joined in the distilled water of its weight 20 times, stir, add hemicellulase, Enzymolysis 18 minutes at 50 DEG C, reducing temperature is 26 DEG C, adds above-mentioned iron salt solutions, is incubated 30 minutes, adds the hydrogen-oxygen of 3mol/l Changing sodium, regulation pH is 5, adds above-mentioned epoxychloropropane, and rising high-temperature is 70 DEG C, and insulated and stirred 30 minutes adds 3mol/l's Sodium hydroxide, regulation pH is 10, stirring reaction 30 minutes, obtains epoxide modified Semen sojae atricolor latex；
(5) taking above-mentioned epoxide modified Semen sojae atricolor latex, be passed through nitrogen, rising high-temperature is 70 DEG C, adds above-mentioned N methylol acryloyl Amine, drips acetic acid, and regulation pH is 5, and insulated and stirred 60 minutes obtains acid amide-grafted epoxy soybean latex；
(6) taking above-mentioned acid amide-grafted epoxy soybean latex, mix with silicon dispersion liquid, add nylon acid methyl ester, at 80 DEG C, insulation is stirred Mixing 10 minutes, add above-mentioned polyvinyl alcohol, rising high-temperature is 76 DEG C, and insulated and stirred 20 minutes adds above-mentioned styrene weight 20%, the 18% of above-mentioned potassium peroxydisulfate weight, stirring mixing 10 minutes, drip remaining styrene, potassium peroxydisulfate, reducing temperature is 40 DEG C, insulation reaction 60 minutes, cooling, obtain Polystyrene grafting rubber made from soybean cake；
(7) above-mentioned Polystyrene grafting rubber made from soybean cake is mixed with remaining each raw material, stir, to obtain final product.
Performance test:
Viscosity 4.94Pa.s；
Bonding strength: 1.23 Mpa.

Claims (2)

1. a Ludox soybean-based sheet material adhesive, it is characterised in that it is made up of the raw material of following weight parts:
Polyvinyl alcohol 2-4, defatted soybean flour 170-200, iron chloride 0.3-0.4, ferrous chloride 0.1-0.2, epoxychloropropane 0.8-1, N hydroxymethyl acrylamide 2-3, styrene 16-20, potassium peroxydisulfate 0.1-0.2, hemicellulase 3-4, poly-diphenyl The hydrochloric acid solution 60-70 of methane diisocyanate 10-19,20-30%, pyromellitic acid dianhydride 0.6-1, Sodium fluoroborate 2-3, positive silicon Acetoacetic ester 6-8, hexadecyltrimethylammonium chloride 0.7-1, nylon acid methyl ester 2-3, calcium stearate 1-2.
2. the preparation method of a Ludox soybean-based sheet material adhesive as claimed in claim 1, it is characterised in that include with Lower step:
(1) by above-mentioned iron chloride, ferrous chloride mixing, join in the hydrochloric acid solution of 20-30%, stir, obtain iron salt molten Liquid；
(2) by above-mentioned hexadecyltrimethylammonium chloride, Sodium fluoroborate mixing, join compound weight 28-30 times go from In sub-water, stirring, rise high-temperature and be 70-76 DEG C, insulated and stirred 10-15 minute, the hydrochloric acid of dropping 96-98%, regulation pH is 2-3, continues insulated and stirred 20-30 minute, adds above-mentioned calcium stearate, and stirring, to room temperature, obtains acid dispersion；
(3) above-mentioned tetraethyl orthosilicate is joined in the deionized water of its weight 17-20 times, stir, add PMA Dianhydride, rises high-temperature and is 60-67 DEG C, add above-mentioned acid dispersion, insulated and stirred 1-2 hour, obtain silicon dispersion liquid；
(4) above-mentioned defatted soybean flour is joined in the distilled water of its weight 20-27 times, stirs, add hemicellulase, Enzymolysis 18-20 minute at 50-55 DEG C, reduces temperature and is 26-30 DEG C, add above-mentioned iron salt solutions, be incubated 30-35 minute, add Entering the sodium hydroxide of 3-5mol/l, regulation pH is 5-6, adds above-mentioned epoxychloropropane, rises high-temperature and is 70-75 DEG C, and insulation is stirred Mixing 30-35 minute, add the sodium hydroxide of 3-5mol/l, regulation pH is 10-11, stirring reaction 30-40 minute, obtains epoxide modified Semen sojae atricolor latex；
(5) take above-mentioned epoxide modified Semen sojae atricolor latex, be passed through nitrogen, rise high-temperature and be 70-75 DEG C, add above-mentioned N-methylol propylene Amide, drips acetic acid, and regulation pH is 5-6, and insulated and stirred 60-60 minute obtains acid amide-grafted epoxy soybean latex；
(6) take above-mentioned acid amide-grafted epoxy soybean latex, mix with silicon dispersion liquid, add nylon acid methyl ester, be incubated at 80-90 DEG C Stir 10-15 minute, add above-mentioned polyvinyl alcohol, rise high-temperature and be 76-80 DEG C, insulated and stirred 20-30 minute, add above-mentioned benzene The 20-25% of weight ethylene, the 18-20% of above-mentioned potassium peroxydisulfate weight, stirring mixing 10-20 minute, drip remaining styrene, Potassium peroxydisulfate, reduces temperature and is 40-45 DEG C, insulation reaction 60-70 minute, cooling, obtains Polystyrene grafting rubber made from soybean cake；
(7) above-mentioned Polystyrene grafting rubber made from soybean cake is mixed with remaining each raw material, stir, to obtain final product.
CN201610656551.2A 2016-08-12 2016-08-12 A kind of Ludox soybean-based sheet material adhesive and preparation method thereof Withdrawn CN106189953A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109016051A (en) * 2018-09-10 2018-12-18 余姚市合丰厨具有限公司 A kind of novel reed plate

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109016051A (en) * 2018-09-10 2018-12-18 余姚市合丰厨具有限公司 A kind of novel reed plate

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Application publication date: 20161207